Metal nanoclusters stabilized by N‐heterocyclic carbene (NHC) ligands have attracted increasing interest for their special structures and diverse applications. However, developing synthetic strategies and extending the database of NHC‐protected nanoclusters are still challenging tasks. In this work, a novel and rapid synthetic method is developed to prepare AuAg alloy nanocluster ligated by carbene based on the reactivity of nanoclusters. The rod‐like carbene‐capped bimetal nanocluster, [Au13Ag12(PPh3)8(BMIm)2I8]SbF6 (Au13Ag12:BMIm), was achieved and characterized by a series of techniques. The alloy nanocluster consists of two vertex‐sharing icosahedrons and carbene ligands, phosphine ligands, and I atoms. Interestingly, the introduced carbene ligands show strong coordination capabilities with Au, enhancing the interaction between metal core and ligands. To the best of our knowledge, the carbene‐capped Au13Ag12:BMIm nanocluster is the first of its kind to show higher thermostability and higher sensitivity to light compared with the homogeneously capped analogue nanocluster ([Au13Ag12(PPh3)10I8]SbF6). Density functional theory calculations attribute these properties to a unique delocalization of electrons within the frontier orbitals. Finally, the Au13Ag12:BMIm anchored on NiFe‐LDH exhibits remarkable electrocatalytic activity in the electrosynthesis of urea from NO3− and CO2, achieving a urea production rate of 29.5 mmol gcat–1 h–1 with a Faradaic efficiency of 34% at ‐0.5 V (vs. RHE).

中文翻译：

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卡宾配体如何转化 AuAg 合金纳米团簇用于电催化尿素合成


由 N-杂环卡宾 （NHC） 配体稳定的金属纳米团簇因其特殊的结构和多样化的应用而引起了越来越多的兴趣。然而，开发合成策略和扩展受 NHC 保护的纳米团簇数据库仍然是一项具有挑战性的任务。本工作基于纳米团簇的反应性，开发了一种新颖、快速的合成方法，制备卡宾连接的 AuAg 合金纳米团簇。棒状卡宾封端双金属纳米团簇 [Au13Ag12（PPh3）8（BMIm）2I8]SbF6 （Au13Ag12：BMIm） 通过一系列技术获得并表征。合金纳米团簇由两个顶点共享的二十面体和卡宾配体、膦配体和 I 原子组成。有趣的是，引入的卡宾配体表现出与 Au 的强配位能力，增强了金属核和配体之间的相互作用。据我们所知，与均匀封端的模拟纳米团簇 （[Au13Ag12（PPh3）10I8]SbF6） 相比，卡宾封端的 Au13Ag12：BMIm 纳米团簇是同类产品中第一个表现出更高的热稳定性和更高的光敏感性的纳米团簇。密度泛函理论计算将这些特性归因于前沿轨道内电子的独特离域。最后，锚定在 NiFe-LDH 上的 Au13Ag12：BMIm 在 NO3− 和 CO2 电合成尿素中表现出显着的电催化活性，在 -0.5 V 下实现了 29.5 mmol gcat–1 h–1 的尿素生成速率和 34% 的法拉第效率（相对于 RHE）。